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Methylammonium Lead Bromide Perovskite Battery Anodes Reversibly Host High Li-ion Concentrations Nuria Vicente, and Germà Garcia-Belmonte J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.7b00189 • Publication Date (Web): 13 Mar 2017 Downloaded from http://pubs.acs.org on March 13, 2017

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The Journal of Physical Chemistry Letters

Methylammonium Lead Bromide Perovskite Battery Anodes Reversibly Host High Li-ion Concentrations Nuria Vicente and Germà Garcia-Belmonte* Institute of Advanced Materials (INAM), Universitat Jaume I, 12006 Castelló, Spain Corresponding author’s e-mail: [email protected] (G. G.-B) Abstract Ions migrate through the hybrid halide perovskite lattice allowing for a variety of electrochemical applications as perovskite-based electrodes for batteries. It is still unknown how extrinsic defects as lithium-ions interact with the hybrid perovskite structure during the charging process. It is shown here that Li+ intake/release proceeds by topotactic insertion into the hybrid perovskite host, without drastic structural alterations or rearrangement. Even the perovskite electronic band structure remains basically unaltered upon cycling. The occurrence of conversion or alloying reactions producing metallic lead is discarded. Stable specific capacity ≈200 mA h g-1 is delivered which entails outstanding Li-ion concentration, x in LixCH3NH3PbBr3, approaching 3. Slight distortions of the perovskite lattice upon cycling explain the highly-reversible Li+ intercalation reaction that also exhibits an excellent rate capability.

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Hybrid perovskites have emerged as a family of multifunctional materials with applications in photovoltaics,1-2 optoelectronics,3-5 lasers,6-7 and electrochromism.8 Besides the interesting electronic and photonic properties exhibited by hybrid perovskites, ionic migration allows for a variety of application in electrochemical devices. Ion transport within the lattice of perovskite compounds have applications in solid-oxide fuel cells and oxygen permeation membranes.9-10 It is also known that hybrid perovskites behave as charge storage materials for lithium-ion battery anodes.11 In addition, native defects in hybrid lead halide perovskite materials are able to migrate within the perovskite structure because of the soft character of the compounds.12 Despite the relevance extrinsic ion reaction with hybrids perovskites might have on their potential use in electrochemical devices, only a few works have addressed that issue.11 How lithium-ions interact with the hybrid perovskite structure during the charging process is still an open question.13 It is revealed here that perovskite-based electrodes exhibit high stability upon electrochemical cycling without severe distortions of the crystal structure. This fact indicates a topotactic intercalation for Li+ storage into the perovskite host, without drastic structural alterations or rearrangement. Lithiation proceeds in such a way that several Li-ions are hosted within the same unit cell of the crystal lattice (LixCH3NH3PbBr3) with x approaching 3. Moreover, the occurrence of conversion or alloying reactions producing metallic lead can be discarded. In the present work, the hybrid perovskite CH3NH3PbBr3 has been utilized as active material for the anode electrodes. Its interest in energy storage is related to their 3D framework of corner-connected MX6 (M = Pb, X = Br) octahedrons with organic methylammonium cations located between them (Figure 1d). The hybrid halide perovskite AMX3 can be then regarded as a compact structure in which the dimensionality of Li+ transport is 3D, similarly to that occurring for spinels such as LiMn2O4 in contrast to low-dimension insertion compounds. We present here promising preliminary results and progress into the understanding of the electrochemical charging of nanostructured lead halide perovskite materials, which exhibit rather stable specific capacity ≈200 mA h g-1 with an excellent reversibility. Rate capability between 1 C and 0.25 C charging rates does not significantly change, enabling for high-power performance. Although exhibiting similar electrochemical response, the issue of the underlying intercalation mechanism is not addressed by the previous works on perovskite-based anodes.11 Starting material were synthesized by slow evaporation of N, N-dimethylformamide (DMF, Sigma-Aldrich) in a solution containing stoichiometric amounts of lead bromide (PbBr2, TCI) and methylammonium bromide (CH3NH3Br, >98% TCI) 1M in DMF. First PbBr2 and CH3NH3Br were dissolved in DMF, and then the solution was heat up 90 ºC in magnetic stirring in a close bottle for 12 hours. Solid precipitated is orange color at the end of the reaction. The solution was stirred with a spatula to ensure the evaporation process of trapped solvent. Finally, it was taken out and cooled down to room temperature naturally. XRD to confirm the pure perovskite crystallographic were


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measured using Bruker AXS-D4 Endeavor Advance X-ray diffractometer using Cu Kα, wavelength λ=1.5406 Å. To fabricate the working electrode, the homogeneous slurry was prepared by mixing CH3NH3PbBr3, conductive carbon black (Super P) and poly(vinylidenedifluoride) binder (PVDF, Sigma-Aldrich) with a 80:10:10 weight ratio, respectively, by using Nmethyl-2-pyrrolidone (NMP) as solvent. The slurry was coated on a copper foil by doctor blade and dried at 100ºC overnight. Composite electrodes slices with a diameter of 10 mm were cut and used as working electrodes for structural investigation and electrochemical analysis. To investigate the lithium storage performance of the anode under study, a twoelectrode Swagelok cell-type was used. Li metal foil was used as the counter and reference electrode and an electrolyte-soaked, microporous monolayer membrane (Celgard 2500) was employed as separator. The electrolyte is 1M of hexafluorophosphate lithium slat (LiPF6, Sigma-Aldrich) dissolved in ethylene carbonate, ethyl-methyl carbonate and dimethyl carbonate (EC:EMC:DMC, SigmaAldrich) with 1:1:1 v/v. Cell assembly was carried out in a N2 filled glovebox. For electrochemical characterization, a PGSTAT-30 potentiostat from AUTOLAB equipped with an impedance module was employed. Cyclic voltammetry (CV) was performed in the voltage range from 0.01 to 2.00V with a rate of 5 mV s-1. The constant current charge and discharge profiles of the battery in the voltage range from 0.01 V to 1.80 V at different rates of 50, 100 and 200 mA g-1. All the data are normalized to the load CH3NH3PbBr3 mass. It is shown in Figure 1a XRD patterns of CH3NH3PbBr3 powders fabricated by means of the procedure previously described. It can be indexed as a cubic perovskite structure with a =5.9394 Å (space group = Pm-3m). Diffraction peaks are assigned similarly to those appearing in previous publications.16 It is shown in Figure 1S (Supporting Information) how diffraction peak positions remain unaltered upon lithiationdelithiation, which informs on the integrity of the structure. Recent XRD analyses on CsPbBr3 films after electrochemical doping reveal slight increase of the lattice constant as a consequence of lithiation, signaling negligible structural variations.8 Figure 1b and Figure 1c show SEM images of pristine CH3NH3PbBr3 anodes. Most particles are regular and uniform with average size around 65 nm. Electrode surface is uniform although some pinholes are observed within which secondary particle agglomeration occurs. It is noted here that our synthesis produces nanometer-sized particles different from those reported in previous work,11 which shows the formation of large micrometersized structures by hydrothermal methods. With the aim of investigating the chemical stability of the lead bromide perovskite upon cycling, a detailed ex-situ XPS analysis at different charging states during the first charge-discharge cycle is shown in Figure 1e and Figure 1f. Samples were washed out by anhydrous dimethyl carbonate (DMC) solvent several times, and dried in a vacuum chamber at 60°C for 2 h previous XPS analysis.14 Here two elements are analyzed:



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bromine and lead. XPS spectra for different samples were studied using a C peak at 285.0 eV as reference, which allows identifying the valence states of the elements in pristine and cycled electrodes. In all studied electrodes, the XPS spectrum of lead appears as Pb+2 (Pb 4f) in Figure 1e, and exhibits two peaks attributed to Pb 4f7/2 and Pb 4f5/2 levels at binding energies (BE) of 138.7 eV and 143.6 eV, respectively. This is in full agreement to values reported previously.15-16 In no case it is observed any signal corresponding to metallic lead (Pb0). A recent analysis on CsPbBr3 large single crystals has detected the presence of Pb0 by electrochemical lithiation but using much wider (-5 V1, and simultaneously (ii) it exhibits small structural distortions (topotactic intercalation). Importantly, the rate capability does not exhibit significant reduction for charging currents between 1 C and 0.25 C, indicating the potentiality of perovskite-based materials for high power battery applications. Our findings reveal the outstanding electronic and ionic properties of lead halide perovskites, and their potential use as energy storage materials.

Associated Content Supporting Information Additional XPS spectra, and XRD analysis of lithiated and delithiated electrodes. Author Information. Corresponding author *E-mail: [email protected] ORCID Nuria Vicente: 0000-0002-9823-7131 Germà Garcia-Belmonte: 0000-0002-0172-6175 Acknowledgments We thank financial support by Generalitat Valenciana under Prometeo Project (PROMETEO/2014/020), and Ministerio de Economía y Competitividad (MINECO) of Spain under Project (MAT2016-76892-C3-1-R). N.V. acknowledges University Jaume I through FPI Fellowship Program (PREDOC/2015/54). SCIC from Universitat Jaume I is also acknowledged. The authors acknowledge Celgard for supplying separator membranes.

References (1) Kim, H.-S.; Lee, C.-R.; Im, J.-H.; Lee, K.-B.; Moehl, T.; Marchioro, A.; Moon, S.-J.; Humphry-Baker, R.; Yum, J.-H.; Moser, J. E.; et al. Lead Iodide Perovskite


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